Dyestuffs of the dibenzanthrone series and process of making same



Patented Feb. 28, 1933 UNITED-I STATES PATENT" OFFICE WlIIiHELM mosim, or simian, NEAR BAsEL, SWITZERLAND; AssIcNon r THE man or SOCIETY or CHEMICAL INDUSTRY IN pasts, OFIBASEL, swrrzs31.1mm

DYESTUFFS or THE DIBENZANTHRONE snares AN rnoo sss OF MAKING SAME No Drawing. Application filed October 3, 1931,-Seria1 No. 566,8-12,' and in Switzerland October 14, 1930.

The present invention relates to the manufacture of new dyestufis of the dibenzanthrone series containing chlorine and bromine and dyeing tints which are fast to 5 water. It comprises the process of making these dyestuffs, as well as the dyestuffs themselves.

In United States Patent No. 1,7 7 1,802 dyestuffs are disclosed which dye navy blue shades fast to water. These dyestufis are produced by chlorinating dibenzanthrone between 100 and 160 C. in presence of nitro-' benzene.

These dyestuffs vcontain at least about 3 atoms of chlorine. The positions where these chlorine atoms are fixed in the dibenzan- I throne molecule are not known.

According to the present invention the products obtained by the said manufacture or less" greenish hue. The higher the temperature andthe greater the proportion ofbromine, themore green blue and the richer in bromine is the dyestufl. The analyses of the products show that they contain about' l to 5 halogen atoms, of which at least 3 are chlorine atoms and at least 1 bromine.

The new products'are dark powdersfdissolve in sulfonic acid to blue-violet solutions, in caustic. alkaline hydro'sulfite solutions to greenish blue solutions, and dye cotton from the vat the statedtints. V i The following examples illustrate the invention, the parts being by weight unless otherwise stated. v

a 20 partsof the chlorinated dibenzanthrone, which can be obtained as described in Example 1 of U. S. Patent No. 1,771,802, are

dissolvedin 200 parts ofchlor osulfonic acid at ordinary'temperature. There are added to the solution, whilefstirring, 0.5 part of iodine, or the corresponding quantity of sul fur, and 12.;partsof bromine; -While still stirring, the whole is heated to 55 C. and is kept at 5560 C. until all the bromine has been consumed. .The mass isthenpoured uponice and the dyestuff isolated asusual. There is obtained a blue violet powder which 7 dyes cotton in a greenish blue vat clear green blue tints. The dyeing is excellently fast and, above all, completely. fast to water. The dyestuff dissolves instrong sulfuric acid to a blue- Violet solution, which is considerably more blue thanthat "of, the parent material.

Fromthis solution "water precipitates green blue flocks. Insolvents of high boiling point, such as nitrobenzene, the dyestufi' dissolves to a red violet solutionhaving aslightly red fluorescence. The analysis shows that a trichlormonobromedibenzanthrone is present.

Instead of a chlorosulfonic acid, othersuitable solvents may be used, such as fuming sulfuric acid. 1 1 f 1 'If in thebromination more bromine is used, for example24 parts and. preferably at a raised temperature, there is obtained a product thehalogen content; of which COT"? responds to that of a trichlordibrome-dibenzanthrone, and possessing the. above mentioned dyeing properties.

Ewample 1 kilo of the dyestuff made as described in Example 1 is made into a paste with 100 grams of Turkey red oil andmixed with 100 litres of water at 60 (1.; 5 litres of caustic sodasolution of 36 B. are added and there are strewn into the liquor 2.5 kilos of hydrosulfite conc. powder. The vatting is completeafter 10 minutes. .v

A dye-vat is prepared from 1000 litres of water containing so much caustic sod-a that the dye-bath contains 16 cc. of caustic soda ishbluetints fast to water, which dibenzan- I thrones contain at least 3 atomsof chlorine and at least one atom of bromine, the said products being dark powders, and dissolving in sulfuric acid to blue-violet solutions. In witness whereof I have hereunto signed my name this th da 1 of September 1931. WI HELM MOSER.

solution of36 B. per litre (including the caustic soda solution of the stock vat) after heating to 60 C. any lime compounds are skimmed off and the vat is sharpened ing to the depth of tint required by additi-on 'of hydrosulfite conc. powder. In general, there is used for bright tints, l'kilo, for medium tints0.5 kilo and for dark tints 0.2

' 7 kilo of hydrosulfite conc. powder per 1000 litres of dye-vat. The stockvat is now mixed with the dye-vat and the well boiled and accordwetted cottonis entered,-dyeing being icon 7 'tinued for hour to l hour' at 60 C. The dyed goods are rinsed in water containing a little hydrosulfite, soured, again rinsed and developed at the boil bytreatment with 3 grains of soap and 1 gram of-calcined sodium carbonate perlitre of water for hour. WhatI claim is p 7' 1. A process for the manufactureofnew dyestuffs of the dibenzanthrone series containin chlorine and 'bromineand dyeing tints astto water, consisting'in brominating the dyestuffs dyeing navy blue tints fast 3. A process for the manufacture of new dyestuffs of the dibenzanthrone series containing chlorine andbromine and dyeing tints fast to'water, consisting in brominating the dyestuffs dyeing navy blue tints fast to water, which are produced by chlorinating violanthrone between and 160 C. with chlorine gas in presence of nitrobenzene in. chl-orosulfonic acid in presence of iodine,

I As new products the chlorine and bromine containing at least'tetrahalogenated 'dibenzanthrones dyeing cotton blue to green- 1 iso 

